Production of synthetic resin molding compositions



' for example 4-6%.

Patented July 19, 1949 PRODUCTION OF SYNTHETIC RESIN MOLDING COMPOSITIONS John Allan, Spondon, near Derby, England, as-

,signor to Celanese Corporation of America, a

corporation of Delaware No Drawing. Application October 9, 1946, Serial No. 702,103. In Great Britain October 23, 1945 7 Claims.

This invention relates to moulding compositions and moulded products and has as its principal object to produce materials of high impact strength.

The moulding compositions of the invention comprise unspun staple-fibres of regenerated cellulose of high tenacity and of average length at least 0.75 inch, impregnated with a synthetic resin. By "high tenacity is meant a tenacity of at least 3 gms. per denier.

Preferably the fibres are impregnated with a solution of the synthetic resin in a volatile solvent which is subsequently removed. It is of advantage to carry out the impregnation under fiuid pressure, and to this end the mass of fibres may be enclosed in a vessel which is then evacuated, and to which the impregnating solution is admitted at atmospheric pressure or preferably under super-atmospheric pressure. The impregnating solution may contain, in addition to the synthetic resin, any hardening agents, catalysts, mould lubricants, colouring agents or other substances adapted to facilitate moulding or. to modify the properties of the mouldings obtained. In converting the wet mass of impregnated fibres to a dry moulding composition, it is best to remove most of the solvent by evaporation first at ordinary temperatures, then at higher temperatures, and to separate the fibres from one another while they still reain a proportion ofresidual solvent, This residual solvent makes it easier to separate the fibres without damage such as would result in lower impact strength in the mouldings. It is important with a view to obtaining a composition from which mouldings of high impact strength can be produced, to avoid subjectingthe fibrous mass during or after impregnation to mechanical treatment such as would substantially shorten the fibres. The invention may be illustrated as follows: The fibrous material comprises staple fibres about 1 inch in length of a high tenacity obtained by stretching dry spun cellulose acetate yarn in wet steam or hot water to a tenacity of 6-8 grams per denier, completely saponifying the stretched yarn and cutting it into staple fibres. Yarn waste such as is obtained in the processing of such stretched, saponified yarn, can be cut up to form the fibrous material for the present invention. The staple fibre yarn is fed on to the perforated false-bottom of a pressure vessel having at the top a valve-controlled outlet connected with a vacuum line, and a relief valve set to open at about 60 lbs. per square inch, and at the bottom, below the false bottom, 2 valve-controlled inlets, one connected to a reservoir containing the resin solution and the other to a compressed air main. After introduction of the fibrous material the vessel is evacuated. The outlet valve is then closed and the inlet valve to the resin solution is opened, causing the resin solution to be forced under atmospheric pressure through the perforations in false bottom.

The composition of the resin solution used is as follows, the parts being by weight:

75 parts of a synthetic resin which is a condensation product of phenol and acetaldehyde in approximately equimolecular proportions, the condensation having been carried out in the presence of an acid catalyst.

15 parts of hexamethylene tetramine.

3 parts of aluminium stearate.

180 parts of industrial alcohol.

The synthetic resin is formed by slowly addin 250 parts of paraldehyde to 500 parts of phenol containing about 1% of concentrated hydrochloric acid as catalyst, the temperature being maintained at about 50 C. during the addition, raising the temperature to 98-100 C. when the "reaction mix separates into an aqueous and resinous layer, and continuing the heating for about half an hour at about 120-130 C. The resin obtained is washed free from acid with warm water, separated and the remaining moisture removed by vacuum distillation at a temperature of about 100 C.

When the vessel is nearly full, the supply of resin solution is cut off and the compressed air inlet valve is opened. Air is supplied at a pressure slightly in excess of lbs. per square inch so that it bubbles through the perforations in the false bottom and escapes through the relief valve, and in so doing stirs the contents of the vessel. After thorough impregnation with the resin solution, the fibrous mass is removed, centrifuged, and dried slowly to an alcohol content "of about 5%. The drying can be eflfected at temperatures between 20 and C. for instance by exposure for 24 to 48 hours to atmospheric temerature followed by a short exposure to a temperature of to C. Any adhesion between the fibres is then broken down, for example'by treatment in a rotating arm disintegrator, care being taken to avoid any substantial shortening of the fibres in this treatment.

The fibrous material is then further dried free from-volatile solvent at about 55 to 65 C. The moulding composition so obtained has approxii'nately the following composition, the parts besource of formaldehyde such as hexamethylene ing by weight: tetramine in the moulding composition.

43 4 ts f th 5 nthetic resin The regenerated cellulose material of high tepar e y nacity may be used in conjunction with other 3:3: :2 gg tetmmme 5 fillers for the plastic, for example wood flour or othercellulo's-ic filler orza min'e-ral filler, for exparts ofalunnmumflsteamte '=ample-asbestos in the fomn of fioats or filbres. From s Composition a Standard impact White or coloured pigments may also be employed strength test bar is moulded at 160 C. and 2 tons in the composition. per square inch pressure for 5 minutes. WhenM lnsteadof using the high tenacity regenerated subjected to the Izod notched har im-p ct -cellulose fibresobatained by the saponification of Strength test, it is found t0 e an impact 'high tenacity fibres of cellulose acetate. high strength in eXceSS 0 10 t-l pe tenacity regeneratedcellulose fibres produced in notch. Moulding compositions i-nade in=aisimilar othei w'ays may beemployed. Thus, for example, way but under such conditions that the fibroustenacity regenerated cellulose fibres may be material is exposed to mechanical treatment lobtained by i m t m Cellulose derivawhich substantially shortens the fibrespas for :ex- -tives' such -as viscose' into baths in which the celample when impregnation is carried out in an lulose is regenerated, the materials being internal mixer or in a Hollander miXenonTin stretched considerably during their formation to mixing rolls, were found to give mouldings of very produce the desired high tenacity; or high tenacmuch lower impact strength. itymaterials of regeneratedicelluloselmay:boob- The iv p n 'f fibrev n yn he ic "tained by the zcuprammoniumcpnocess; the-cm r in m y v ri d-"f r ins' n by varying he terials again bein stretched xzonsiderablyvdming concentrationof the 're'sin solution. Preferably their formation. The best results, hUWBVGHLh me ithe concentration of"hexalmethylene' tetramine 'rbeen'bbtainedbyrthejuse tuflfmat'em ails prodw ed and of :mould lubricant should be varied in about bythe saponific'ationr'of- :highatenacity materials the same proportionswasthe concentration of 'of dry spun celiulose 'acetatevswhich 11aye-*been resin. Typical-impact strength figures obtained stretched to'ra considerabletdegreemorexample with compositions accord-ing to the invention ito 5110 10 or 20 times daheiraoriginal ilength or'even containing various-'proporti-onsrof fi-bre' -are shown =1 more, under the influencerif steammr hot water. in the following table, the percentages being by This-'method of 'producing thrhigh tenacityafibre weight and theimp'act' strength being expressed enables fibres of very lowiextensibility tomberfobin ft. lbs/inch of notch w hen-rnea sured by' the tained. Thug-the extension'rzatszbreaki'maywb Izod method. from about 5or6:% orrevenlessiz'o about.8m- 9.% Table of the zoriginal lengith. "-ntherrnethodsofzmaking hi h tenaciwi rcgenerated ceillflosefibresinvoly- Resin Fibre nramgghyien alum ium Average mgstretchmggivesfibres.oi-iowrextensibilityal- Per 3, Per Gait :lgggafi I %t f 5 1531 though figures of-suchaslowzmrder .asmhoser-referred to above are. obtained by. those 'methods. The extensibility-of:the fibres appears to -have an: imporitant =bearing am the "impact strengthobtainable.

Especially valuable results haveszbeenf: obtained when-the regenerated mellixlose' of which the In making the synthetic resin for-the moulding to fibres immposefi 1 moleoulart-wei compositions of the inventiomthe.molecularratio Show PS v flosityofrsolntionsioii:the'zreof acetaldehyde-to-phenol is preferably as de- \generaiedwlnlflset acity fibres ot'i rescribed above, about 1:1; hutit may be slightly generated lcenwoseibfihlghimulewlarlweigntacan less or slightly greater, e. about 12511 be -made by saponrficatiom:underziconditionsiin down to about 1:1.25 or 111.5; the proportion'ofbu which degmdatibn ised, hi'gh tenacity hexa methylene tetramine employed being "infibres of Thigh fi t el creased when the molecular ratio of acetaldehyde 3' ceruulose' tate Isuch jtlsat al S t 0n 111 to phenol is below 1:1. The total molecularratio at-fi fls has a viscosity 0f acetaldehyde employed plus firm-aldehyde compared with glycerineatzthe sameltemperature available in the hexamethylene tetraminej .t0'=55 of'atvleast" Y Wof-themellulose phenol employed should notbe less than 1:1. .Alacetate employed m i' e ebetween though it is preferred to employ a ce'taldehydei in E 90 1 even-2Qfl% 0 m0re whenlneasured forming the themmsemng -Synthetic reSimV-ry as= ascribed-above. Thetenamty nfithe'regensefu] ,results Canibe Obtained using formaldehyde erated cellulose fibres must: iherafi zleasti zthree instead, in the same molecular proportions relaflo gt rand is'i eieraibly bonsidenably tive to the phenol as have'been indicated above h 9 example{fronl 0W3 ifl s' D l for acetaldehyde. By condensing formaldehyde demer more- The extenswn at break is prefer- .With phenol in the mdlecularumtiopof about-3'32 ably o f thelow"orderrefenredtofaboye. For 'fibces in the presence of an alkaline catalyst, .a synof the m ferr d -t mp yr' he theme resin is Obtained which. capable ;r stress/ straincurve:isrsubstantrally'straight-:upato .ening when heated even in the absence of a the 9 'P source f additionayfomamehyde Such as Besides tneni low extensibi lity fibres'zobtain ed amethylene tetramine, that from mou m -by saponifying' high"tenacity fibres-moiv cellulose compositions containingsuc'hi resin the hexetataespeciafly highvis sity ll amethylene tetramine can beomit'ted. A 'long'e q have shown excellent resistance itordegradafionat period of heating, however; is necessary to harden the temperatures t w ie di is ect 511311 resins, and fQr the fpnlrpbse-of "the present G01I lp2tPEd Wifli= other-textilefibres. Inaddition, invention it is preferredtousesynthetic resins thesefibresare of remarlably higlt'wateuresistmade with lower molecular proportionsbf aide ance comparedwith othentextile fibres. hyde, using an acid'catalyst, and to incorporate a the ratio 'ofwet-tena'oity'to dry-tenacity tor such hyde or acetaldehyde.

fibres is commonly as high as 75% and may be much higher, ,e. g. 80-90% These figures are much higher than the corresponding figures for other kinds of regenerated cellulose fibres and for the best natural cellulosic fibres. Mouldings incorporating these more highly-resistant fibres give excellent performance in wet conditions as well as in dry, even when the ratio of fibre to resin -is high and when the conditions of use are such that wear or other slight superficial damage may expose the filling fibres to attack by moisture.

The invention has been described with particular reference to the use as the synthetic resin of a condensation product of phenol and formalde- Other synthetic resins may be used in a similar way, for example similarly constituted condensation products of phenol with benzaldehyde or furfural; or of any of these aldehydes with other phenols, especially mono-nuclear phenols which are unsubstituted in the ortho and para positions to the hydroxy group or to one of the hydroxy groups, for example meta-cresol or resorcinol or with bior multi-functional amino compounds, for example urea, thiourea, guanidine, dicyandiamide, piper- I azine 01 melamine.

The invention, though of particularly utility in the production of mouldings from thermosetting synthetic resins which are condensation polymers, may also be employed in the production of mouldings from other synthetic resins, especially heat-hardening addition polymers of substances containing a plurality of olefinic linkages, e. g. di-allyl phthalate, di-allyl ketone and allyl methacrylate.

Mouldings produced according to the present invention have many uses where a plastic which is resistant to shock is required, for example in the production of machine housings, instrument casings including radio cabinets and clock cases, gear wheels, industrial truck wheels, pulleys, slats for escalators and conveyors, shuttles, shuttleboxes and other loom components, bobbins and other textile package carriers, golf club heads, rifle butts, and protective helmets.

Having described my invention, what I desire to secure by Letters Patent is:

1. Process for the production of a molding composition which comprises impregnating randomly arranged regenerated cellulose staple fibers of tenacity at least 3 grams/denier and of average length at least 0.75 inch with a solution of a synthetic resin in a volatile solvent therefor, evaporating the bulk of the solvent, and breaking down adhesion between the impregnated fibers without substantially shortening the fibers, by mechanical treatment applied while the fibers still contain a small amount of solvent.

2. Process for the production of a molding composition which comprises impregnating randomly arranged regenerated cellulose staple fibers of tenacity at least 6 grams/denier and of average length at least 1 inch with an alcoholic solution of an acid-catalyzed condensation product of a phenol and an aldehyde, evaporating the bulk of alcohol and breaking down adhesion between the impregnated fibers without shortening the fibers, by mechanical treatment applied while the fibers still contain about 5% of alcohol.

3. Process for the production of a molding composition which comprises impregnating randomly arranged regenerated cellulose staple fibers of tenacity at least 6 grams/denier and of average length at least 1 inch with an alcoholic solution of an acid-catalyzed condensation product of a phenol and formaldehyde in substantially equi- .while the fibers still contain about 5% of alcohol.

4. Process for the production of a molding composition which comprises impregnating randomly arranged regenerated cellulose staple fibers of tenacity at least 6 grams/denier and of average length at least 1 inch with an alcoholic solution of an acid-catalyzed condensation product of a phenol and acetaldehyde in substantially equimolecular proportions, said solution containing at least half a molecular proportion, based on the phenol, of hexamethylene tetramine, together with a suitable mold lubricant, evaporating the bulk of the alcohol and breaking down adhesion between the impregnated fibers without shortening the fibers, by mechanical treatment applied while the fibers still contain about 5% of alcohol.

5. Process for the production of a molding composition which comprises impregnating in an evacuated zone randomly arranged regenerated cellulose staple fibers of tenacity at least 6 grams/denier and of average length at least 1 inch with an alcoholic solution of an acid-catalyzed condensation product of a phenol and an aldehyde, the solution being supplied under pressure, evaporating the bulk of the alcohol and breaking down adhesion between the impregnated fibers without shortening the fibers, by mechanical treatment applied while the fibers still contain about 5% of alcohol.

6. Process for the production of a molding composition which comprises impregnating, in an evacuated zone, randomly arranged regenerated cellulose staple fibers of tenacity at least 6 grams/denier and of average length at least 1 inch with an alcoholic solution of an acid-catalyzed condensation product of a phenol and formaldehyde in substantially equimolecular proportions, said solution being supplied under pressure and containing at least half a molecular proportion, based on the phenol, of hexamethylene tetramine, together with a suitable mold lubricant, evaporating the bulk of the alcohol and breaking down adhesion between the impregnated fibers without shortening the fibers, by mechanical treatment applied while the fibers still contain about 5% of alcohol.

'7. Process for the production of a molding composition which comprises impregnating, in an evacuated zone, randomly arranged regenerated cellulose staple fibers of tenacity at least 6 grams/denier and of average length at least 1 inch with an alcoholic solution of an acid-catalyzed condensation product of a phenol and acetaldehyde in substantially equimolecular proportions, said solution being supplied under pressure and containing at least half a molecular proportion, based on the phenol, of hexamethylene tetramine, together with a suitable mold lubricant, evaporating the bulk of the alcohol and breaking down adhesion between the impregnated fibers without shortening the fibers, by mechanical treatment applied while the fibers still contain about 5% of alcohol. JOHN ALLAN.

(References on following page) armw I; REFERENCES-GEE! FOREIGN PATENTS The following references are of record 'in lthe Number Country Date :file of this patent: 1 116,283 Australia Mar. 2, 194A 316,275 Great Britain Dec. 2, 1929 UNITEDISTATES "PAIENTS 1 477,222 Great Britain Dec. 24, 1937 Number Name Date 545,216 Great Britain May 15, 1942 1,223,216 Talley 'Apr. 1'1, 1917 12,168,335 Heckert Aug-18 ,1939 12,240,480 Dillehay V 'May -.6,' 19.41

1-:2,-398;00l Haney Apr. 9, 1946 

